Catalyst for polymerizing olefins

ABSTRACT

A catalytic system for polymerizing olefins comprises: 
     (a) a component containing an organoaluminum compound, and 
     (b) a component containing a titanium halide obtained by: 
     (i) copulverizing a magnesium compound containing halogen or a manganese compound containing halogen with at least one electron-donor compound to produce a copulverized product, 
     (ii) treating the copulverized product with an ether to produce a treated product, and 
     (iii) reacting the treated product with a titanium chloride. 
     The novel catalytic system is useful for polymerizing olefins such as ethylene and propylene. 
     A process for producing the component containing a titanium halide is also provided.

BACKGROUND OF THE INVENTION

This invention relates to a catalytic system for polymerizing olefins, anovel component of the system containing titanium halide, a process forpreparing the novel component containing titanium halide, and the use ofthe system in polymerizing olefins, especially propylene.

The polymerization of olefins by coordinate complex catalytic systems,often termed Ziegler-Natta catalysis, has been well-known for over 25years. Generally, there are two components in this type of system: onebased on an organoaluminum compound or its substitute, the othercontaining a titanium or other transition metal halide. Althoughthousands of such catalytic systems have been disclosed, there is alwaysa quest for improvement in two important properties: activity andisotactic index.

Activity is measured by the grams of polyolefin produced per gram oftitanium component or other transition metal component employed in thecatalytic system. The higher the activity, the lower the amount ofmetallic ash and corrosive halide left in the polymer. If the activityis high enough, e.g. ≧3,000, then the de-ashing step in processing thefinal polyolefin can be omitted--an important improvement.

For olefins, such as propylene, which can form isotactic structures, thehigher the isotactic index, the better the physical properties of thepolymer. Isotactic polypropylene is more ordered, less soluble inhalocarbons or hydrocarbons, and useful for its higher strength than themore soluble atactic form. Isotactic indices of 93 or higher are favoredfor commercial polypropylene. ;p Previously Kashiwa et al. disclosed inU.S. Pat. No. 3,642,746 a process for polymerizing olefins by means of acatalytic component supported on a metal dihalide, which had beentreated with an electron-donor compound and then reacted with eithertitanium tetrachloride or vanadium tetra- or pentachloride. Among theelectron-donor compounds are aliphatic and cyclic ethers.

Yamaguchi et al. disclose in U.S. Pat. No. 3,989,881 a component usedfor polymerizing olefins comprising a solid ethereal complex ofmagnesium halide and titanium/vanadium halide, which may be obtained bymilling the ethereal complexes of magnesium halide and the transitionmetal halide.

Hirota et al. disclose in U.S. Pat. No. 4,180,636 a copulverizedpolymerization component obtained by milling a magnesium halide supportwith an aromatic additive, a mixture of titanium tetrahalide and anelectron donor, which may be an ether, plus an organo-aluminum compoundactivated by an aromatic carboxylic ester.

Wagner discloses in U.S. Pat. No. 4,186,107 a coordinate complexpolymerization catalyst employing a component of titanium halide on amagnesium chloride support, prepared by the reduction of a magnesiumalkyl with an aluminum alkyl halide followed by optional post treatmentwith a dialkyl ether.

Sunada et al. in Belgian published patent application No. 880,807 ofApr. 17, 1980 based on Japanese patent application No. 79/152,818 ofNov. 26, 1979 (see C.A., Vol. 93, 240287N) disclose a component for apolymerization catalyst prepared by heating titanium tetrachloride, anether, and an organoaluminum compound in an aliphatic hydrocarbonsolvent containing a haloarene, cooling the mixture below 40° C., addingan ether plus titanium tetrachloride then heating the solution, and thenrepeating the cooling/heating cycle one or more times with repeatedadditions of both ether and titanium tetrachloride.

All five of the disclosures above are incorporated by reference intothis application.

It is an object of this invention to provide a catalytic system forpolymerizing olefins, such as propylene, so that de-ashing may beomitted and product with high isotactic index prepared. Other objects ofthe present invention will be apparent to those skilled in the art.

SUMMARY OF THE INVENTION

Surprisingly, both a high activity and high isotactic index (II) can beachieved by employing the novel catalyst of the present invention forthe polymerization of olefins, particularly propylene. The novelcatalytic system comprises:

(a) a component containing an organoaluminum compound, and

(b) a component containing a titanium halide obtained by:

(i) copulverizing a magnesium compound containing halogen or a manganesecompound containing halogen with at least one electron-donor compound toproduce a copulverized product,

(ii) treating the copulverized product with an ether to produce atreated product, and

(iii) reacting the treated product with a titanium chloride.

For another aspect of the present invention the novel componentcontaining a titanium halide and a process for producing the novelcomponent containing a titanium halide are provided.

For still another aspect of the present invention a process foremploying the novel catalytic system to polymerize olefins is provided.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is broadly applicable to the polymerization ofmonomeric olefins especially 1-olefins including ethylene, dienesespecially conjugated ones such as butadiene, and those other olefinswhich are only marginally polymerizable, such as 2-butene. The preferredmonomeric olefins are those corresponding to the formula R--CH═CH₂,wherein R is an alkyl radical containing up to 12 carbon atoms inclusiveand hydrogen. Among the preferred, monomeric olefins are ethylene,propylene, 1-butene, 1,4-butadiene, 1-pentene, 4-methyl-1 pentene,1-hexene, and the like. These monomers may be employed individually orin comonomeric mixtures such as ethylene/propylene,ethylene/propylene/butadiene, and the like.

Although for illustrating the present invention the polymerization ofpropylene is described herein as an example, the invention is by nomeans limited to any one monomeric olefin.

The component (a) containing an organoaluminum compound is well-known tothose skilled in the art of coordinate complex (Ziegler-Natta) additionpolymerization. The component may be selected from the followingcompounds: trialkyl aluminums such as triethylaluminum,triisobutylaluminum, and trihexylaluminum, dialkyl aluminum halides suchas diethylaluminum chloride, diethylaluminum bromide, anddibutylaluminum chloride, alkylaluminum sesquihalides such asethylaluminum sesquichloride, alkylaluminum dihalides such asethylaluminum dichloride, ethylaluminum difluoride, and butylaluminumdichloride, and dialkylaluminum alkoxides such as diethylaluminumethoxide, diethylaluminum butoxide, and diethylaluminum phenoxide.

An electron donor such as an alkyl ester of an aromatic acid may be usedin conjunction with component (a). Methyl toluate and ethyl anisate areexamples of such electron donors. Electron donors in component (a) areadvantageously used in molar ratio from about 1:10 to 1:1 with respectto the aluminum alkyl.

The first step (i) in obtaining component (b) containing a titaniumhalide is copulverization of a magnesium compound or a manganesecompound or a mixture thereof containing halogen as a support with oneor more electron donors and optionally a pulverization aid.

The preferred support for practicing the instant invention is anhydrousmagnesium dichloride, but other support materials may be selected frommagnesium hydroxychloride, magnesium alkoxychloride, magnesium bromide,magnesium hydroxybromide, magnesium alkoxybromide; manganese chloride,manganese bromide, manganese hydroxychloride, manganese hydroxybromide,and manganese alkoxyhalide. Magnesium phenoxy halide and magnesiumsubstituted phenoxy halides may also be used. Preferred substituents inthe phenoxy moiety are alkyl groups containing 1 to 5 carbon atoms,halogen groups such as chloride or bromine, and the nitro group. As inchloro-substituted phenoxy magnesium compounds, the magnesium ormanganese compound containing halogen need not have the halogen atomdirectly bonded to the magnesium or manganese atom.

The support, chosen from the halogenated materials cited above, may alsobe partially converted to alcoholate or carbonate groups. Furthermore,the support may contain diluents, up to about 70 percent, of inert,powdered material such as inorganic carbonates, sulfates, borates, oroxides. Examples of such diluents are dry NaCl, KCl, LiCl, CaCO₃, BaCO₃,Na₂ SO₄, K₂ SO₄, Na₂ CO₃, K₂ CO₃, Na₂ B₄ O₇, CaSO₄, B₂ O₃, Al₂ O₃, SiO₂,TiO₂ and the like.

The copulverization may be carried out in any suitable milling equipmentsuch as a ball mill, a hammer mill, a vibratory mill, a grinding mill,or the like. The purpose of the copulverization is to bring the reagentsinto more intimate contact than the usual mixing step, which is intendedonly to create physical homogenity. Use of a ball mill is preferred,especially employing stainless steel balls, but ceramic, glass, or ballsof other material may be substituted.

Copulverization may be carried out in the presence of an organic orinorganic pulverization aid which may be simple compounds or polymers.Representative pulverization aids are kerosene, polystyrene,polypropylene, organosiloxanes, boron oxide, silicon oxide and aluminumoxides. Of the cited pulverization aids the polysiloxanes, which alsohave electron-donating properties, are preferred. From about 0.001 toabout equal weight of such pulverization aid may be used in each chargemilled.

The amount of electron-donor compound used in the step (i)copulverization is from about 0.001 to about 1 mole per mole of themagnesium or manganese compound containing halogen acting as thesupport. Preferably, about 0.01 to about 0.1 mole electron-donor permole of support material is used.

Electron-donors are compounds, usually but not necessarily organic,containing one or more oxygen, nitrogen, phosphorus, silicon or sulfuratoms which can form complexes with the magnesium or manganese supportmaterials containing halogen atoms. Often the electron donors are termedLewis bases, since the support materials containing halogen atoms oftenare Lewis acids.

Among the classes of compounds containing oxygen suitable for furnishingelectron-donors are: aliphatic and aromatic ethers, aliphatic carboxylicesters, aromatic carboxylic esters, cyclic esters or carbonic acid,alcohols, phenols, aldehydes, ketones, aliphatic and aromatic carboxylicacids, lactones, and carboxylic acyl halides. Of these the aromaticcarboxylic acids are preferred.

Among the classes of compounds containing nitrogen suitable forfurnishing electron-donors are: aliphatic amines and polyamines,aromatic amines, heterocyclic amines, nitriles, carbamates, aromaticisocyanates, and aromatic azo compounds. Electron-donors containing bothoxygen and nitrogen atoms may be used such as aliphatic and aromaticamides, nitrocompounds, or guanidine and its alkyl-substitutedderivatives.

Other classes of electron-donors include phosphines, phosphoroamides,sulfides, mercaptans, thioethers, thioesters, organoalkoxysilanes,organoaryloxysilanes, aminosilanes, organosilicon isocyanates, andorganopolysilanes, organopolysiloxanes, and polysilazines.

Examples of electron-donor compounds from some of the classes listedabove are: ethyl benzoate, ethyl anisate, ethyl toluate, ethyl acetate,diethyl carbonate, γ-butyrolactone, benzoic acid, toluic acids, acetone,acetophenone, nitrobenzene, veratrol, tetramethylenediamine, dimethylacetamide, methyl carbamate, toluene diisocyanate, benzonitrile,N-methyl pyrrolidone, phenol, and thiophenol. Especially preferred amongthese electron-donors is ethyl benzoate and the toluic acids.

The electron-donor may be placed in the pulverizing apparatus before,during, or after some of the pulverizing time, as long as the supportand the electron-donor are intimately contacted during some of thepulverization. More than one electron-donor may be used and the severaldonors may be added in any convenient fashion. The pulverization aid mayalso function as an electron-donor. The use of from about 0.01 to about1 mole of electron-donor per mole of support material is preferred.

In the process of this invention after the copulverization of amagnesium or manganese support material containing halogen with one ormore electron donors the product is treated with an ether to formunknown amounts of complex treated product.

Treatment with an ether can take place at any temperature between about0° and about 200° C., but a treatment temperature between about 50° and100° C. is preferred depending on the boiling point of the ether.Depending on the temperature of treatment, the treatment time can varyfrom a few minutes to a day or more with shorter treatment times beingmore appropriate with higher treatment temperatures. The preferred timeis from about one-half to about four hours. Especially preferred is atreatment time from one to three hours at about 50° to about 60° C.Normally a large excess of ether is employed as the treating medium, butinert hydrocarbon diluents may also be employed in the ether.

Symmetrical or asymmetrical ethers may be chosen especially those withhydrocarbyl radicals, that is aliphatic, cycloaliphatic or aromaticmoieties. The hydrocarbyl radicals may have substituents, however, suchas halogen, nitro, cyano or other hydrocarbyl groups which arenonreactive during the processing of the catalyst support and thesubsequent polymerization of olefins. The ether may bear heterocyclicgroups such as pyridyl or thienyl.

Some representative ethers suitable for post-treating the copulverizedsupport material are dimethyl ether, methyl ethyl ether, diethyl ether,dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether,diisoamyl ether, dioctyl ether, didodecyl ether, diallyl ether, isobutylvinyl ether, dioxane, lower polyethylene glycols up to about 500molecular weight, lower polypropylene glycols up to about 600 molecularweight, ethylene glycol dimethyl ether, ethylene glycol diethyl ether,ethoxyethoxyethylene glycol ethyl ether, tetrahydrofuran, diphenylether, ditolyl ether, anisole, dimethoxybenzene, tetrahydrofuran. Amongthe ethers aliphatic compounds are preferred. Especially preferred isdi-n-butyl ether.

After treatment with the ether the support material is normallyfiltered, washed with a volatile hydrocarbon solvent such as heptane,and vacuum dried. No one or all of these three steps is necessary,however, for carrying out the process of this invention. If convenient,separation, washing, and drying is preferred.

The third major step in the process of this invention is reaction with atitanium compound in order to prepare the titanium component of thecoordinate complex polymerization catalyst.

The titanium compound employed for the reactive step may be representedby the formula:

    TiX.sub.n (OR').sub.p (NR.sup.2 R.sup.3).sub.q (OCOR.sup.4).sub.r

wherein X is a chlorine, bromine, or iodine atom; R', R², R³, and R⁴ maybe the same or different and are hydrocarbyl radicals having from 1 toabout 12 carbon atoms; n is a number from 1 to 4; p, q, and r arenumbers from 0 to 3, and n+p+q+r is 4.

Some examples of titanium halocompounds useful in performing thereactive step are titanium tetrachloride, titanium tetrabromide,titanium tetraiodide, methoxytitanium trichloride, dimethoxy titaniumdichloride, ethoxytitanium trichloride, dimethylaminotitaniumtrichloride, bis(dimethylamino)titanium dichloride and titanium benzoatetrichloride. Preferably the reactive titanium compound is a liquid, butthis is not necessary if a convenient, inert solvent can be found forthe reagent. The titanium compound can be employed neat or in a suitablesolvent. The ratio of titanium compound to magnesium support materialcan range from about 0.1 to about 100 molar.

Titanium trichloride material may also be used.

The titanium reaction can be carried out at any temperature from about25° to about 200° C., but temperatures from about 75° to about 150° C.are preferred. This reaction can be carried out from a few minutes toseveral hours, but a reaction time of one-half to four hours ispreferred.

After the pulverization, ether-treating, and titanium-reaction steps,the product is preferably separated from the liquid medium, washed withan inert solvent such as heptane, and dried, preferably by vacuum dryingat ambient temperature. Because this supported titanium catalystcomponent is sensitive to air and moisture it should be stored in a dry,inert atmosphere.

The titanium catalyst component which is a product of the process of thepresent invention may be used along with a suitable organoaluminumcompound as a catalyst for the polymerization of olefins such asethylene, propylene, butene and butadiene, or copolymers of theseolefins with each other and other olefins, in the coordinate complex(Ziegler-Natta) type of polymerization in conventional fashion, as iswell-known. This polymerization is illustrated in the Examples. Themolar ratio of organoaluminum compound to titanium in the treated andmodified titanium component of the present invention may range fromabout 2000:1 to about 0.5:1; the preferred molar ratio is from about200:1 to about 100:1.

Having described the present invention above, we now illustrate it inthe following Examples. These Examples, however, do not limit thepresent invention, which may be carried out by other means but stillremain within the scope of the present disclosure.

EXAMPLE 1

This Example illustrates preparation of the titanium component of thepresent invention.

Into a 1-liter stainless steel ball mill were placed 45 g. anhydrousmagnesium chloride, 11 g. ethyl benzoate, 2.8 g. silicone oil (GeneralElectric Co., SF 96-100) and 1750 g. stainless steel 1.5-cm balls. Themill was rotated for 96 hours at about 50 rpm. Ten grams of the productof the pulverizing step was suspended in 100 ml. heptane in a 250-ml.three-necked flask equipped with a magnetic stirrer and a thermometer.The contents were heated to 55° C. and then 10.2 g. di-n-butyl ether wasadded, the temperature being maintained with stirring for two hours.After this treatment step the mixture was cooled, filtered, washed with800 ml. heptane, and vacuum-dried at 0.1 torr for 17 hours (overnight).The product was then sieved through a U.S. standard 140-mesh screen.

An aliquot of 5.1 g. of the pulverized and treated product was thencaused to react with 85 ml. of neat TiCl₄ at 95° C. in a stirred vesselfor about 11/2 hours. The mixture was cooled, filtered, the productwashed with heptane, vacuum dried, and sieved through a 140-mesh screen.The product was 4.4 g. of a pale yellow powder, sensitive to air andmoisture.

EXAMPLE 2

This Example illustrates standard test conditions for slurrypolymerization, one of the techniques for utilizing the presentinvention.

A polymerization reactor in the form of a four-liter, jacketed autoclavewas equipped with a heater, purging ports, thermocouple, and mechanicalstirrer. It was charged with two liters of dry heptane and brought to50°±5° C. A nitrogen purge was commenced, and a weighed quantity of theorganoaluminum compound was added by syringe and stirred for about 10seconds. Then a weighed amount of the electron donor was added throughthe entry port, and the reaction mixture stirred for about 10 secondsagain. At this point the solid titanium component of the catalystsystem, as made in Example 1, was added. Monomer-grade propylene wasthen pumped into the reactor until a pressure of 10 atmospheres wasreached at 65° C. During the polymerization more propylene was added tomaintain the pressure at 10 atmospheres at 65° C. for 11/2 hours, theduration of the standard test.

After the 11/2 hour standard test the polymer was filtered, washed withisopropyl alcohol, oven-dried at 70° C., and weighed, thus giving aweight termed Dry Polymer. In order to determine the amount ofheptane-soluble polymer formed the reaction solvent filtrate wasevaporated to dryness.

EXAMPLE 3

This Example illustrates standard test conditions for bulkpolymerization, another technique for utilizing the present invention.

As in Example 2, a 2.8 l. jacketed autoclave was equipped with a heater,purging ports, thermocouple, and mechanical stirrer. The nitrogen purge,addition of organoaluminum compound, electron donor, and titaniumcomponent of the present invention was carried out as in Example 2. Then2 l. of liquid propylene was added and brought to 70° C. Again thestandard polymerization test was run for 11/2 hours. At the end of thepolymerization time excess propylene was vented from the reactor. Thepolymer was collected, dried at 70° C., and weighed to give the amountof Dry Polymer.

For both the slurry test of Example 2 and the bulk polymerization ofExample 3, the activity of the titanium component of the presentinvention was defined as follows: ##EQU1##

The amount of polymer insoluble in heptane was determined by athree-hour extraction at the boiling point of heptane and termed "C₇ ".Isotactic Index (II) percentage was then defined as: ##EQU2##

EXAMPLE 4

This Example illustrates the use of the component of the presentinvention, prepared in Example 1, to polymerize propylene in a slurry,as described in Example 2.

The procedure of Example 2 was followed employing the followingcatalytic components. The titanium component (catalyst) was 50 mg. ofthe yellow powder prepared in Example 1. The aluminum component(co-catalyst) was a 4:1 molar ratio of 12 mmol triethylaluminum and 3mmol methyl p-toluate.

When the treatment with n-butyl ether was included, the results were5016 g. polypropylene per g. titanium catalyst (activity) and anIsotactic Index (II) of 96.7.

When another standard polymerization was carried out under the sameconditions as above but employing a titanium control catalyst which hadnot received the ethereal treatment of the present invention theactivity/II figures of merit were 5374/95.3.

EXAMPLES 5-9

These Examples illustrate further embodiments of the present invention,all carried as in Example 4, but using different electron donors.

In each case a weighed amount of MgCl₂ was milled with an oxygenatedelectron donor and silicone oil adjuvent under the action of stainlesssteel balls. The product was washed with heptane, sieved, and weighed.

An aliquot of the product was treated with 10.2 g. di-n-butyl ether for11/2 hours at 55° C., washed with 800 ml. heptane, dried, and sieved.Another control aliquot was not treated with ether. Both aliquots werethan individually reacted with 85 ml. TiCl₄ at 95° C. for about 2 hours,washed with 700 ml. heptane, dried, sieved and weighed. The Activity andIsotactic Index for both the product of the present invention and thecontrol are given below:

    __________________________________________________________________________         MgCl.sub.2                                                                        Donor   Milling                                                                            Silicone                                                                           Wgt. Ether                                                                          Wgt. Ether and                                                                        Invention                                                                           Control                        Example                                                                            (g) (g)     Time(hr)                                                                           Oil(g)                                                                             Treated(g)                                                                          Post-Treated(g)                                                                       Activity/II                                                                         Activity/II                    __________________________________________________________________________    5    20  ethyl benzoate                                                                        144  2.8  10    5.3     6752/95.5                                                                           7850/94.1                               2.4                                                                  6    30  benzoic acid                                                                          168  4.2  10    5.2     3644/94.9                                                                           5423/89.1                               0.8                                                                  7    20  o-toluic acid                                                                         164  2.8  5.2   4.0     4502/94.4                                                                           6165/87.6                               0.6                                                                  8    20  m-toluic acid                                                                         144  2.8  5.2   5.1     4761/93.0                                                                           5021/86.1                               0.6                                                                  9    20  p-toluic acid                                                                         139  2.8  5.2   3.5     4386/94.9                                                                           4867/87.9                               0.6                                                                  __________________________________________________________________________

One sees that for the important property of Isotactic Index in each casethe polymerization employing the catalytic titanium component of thepresent invention gives a higher value than the control.

Having illustrated the invention, what we seek by grant of letterspatent may be described by the following claims.

We claim:
 1. A catalytic system for polymerizing olefins comprising:(a)a component containing an organoaluminum compound, and (b) a componentcontaining a titanium halide obtained by:(i) copulverizing a magnesiumcompound containing halogen compound or manganese compound containinghalogen with at least one electron-donor compound to produce acopulverized product, (ii) treating the copulverized product with anether to produce a treated product, and (iii) reacting the treatedproduct with a titanium halide compound.
 2. The catalytic system ofclaim 1 wherein copulverizing step (i) is carried out in the presence ofan effective amount of a pulverization aid.
 3. The catalytic system ofclaim 2 wherein the pulverizing aid is selected from the groupconsisting of hexane, heptane, kerosene, polystyrene, polypropylene,boron oxide, silicon oxide, and organopolysiloxanes.
 4. The system ofclaim 2 wherein the effective amount of pulverization aid is from about0.001 to about 1 times the weight of the magnesium compound containinghalogen or manganese compound containing halogen.
 5. The catalyticsystem of claim 1 wherein the magnesium compound containing halogen ismagnesium dichloride.
 6. The catalytic system of claim 1 wherein atleast one electron-donor compound is an aromatic carboxylic acidemployed in an amount of about 0.01 to about 1 mole of acid per mole ofmagnesium compound containing halogen or manganese compound containinghalogen.
 7. The system of claim 1 wherein at least one electron-donorcompound is an aromatic carboxylic acid having up to 24 carbon atoms. 8.The system of claim 7 wherein at least one electron-donor compound is atoluic acid.
 9. The system of claim 1 wherein at least oneelectron-donor compound is ethyl benzoate.
 10. The catalytic system ofclaim 1 wherein the ether is selected from the group consisting ofaliphatic ethers containing up to 12 carbon atoms, halogenated aliphaticethers containing up to 12 carbon atoms, aliphatic glycol ethers orhalf-ethers containing up to 12 carbon atoms, alicyclic etherscontaining up to 10 carbon atoms, halogenated alicyclic etherscontaining up to 10 carbon atoms, aromatic ethers containing up to 18carbon atoms, and halogenated aromatic ethers containing up to 18 carbonatoms.
 11. The system of claim 1 wherein the ether is a symmetricalaliphatic ether.
 12. The system of claim 11 wherein the symmetricalaliphatic ether is di-n-butyl ether.
 13. The system of claim 1 whereinthe titanium halide compound is titanium tetrachloride.
 14. The systemof claim 1 wherein the titanium halide compound is titanium trichloridematerial.
 15. The system of claim 1 wherein the quantity of titaniumpresent in the component containing a titanium halide is from about 0.1percent to about 10 percent by weight expressed as elemental titanium.16. A component containing titanium halide of a catalytic system forpolymerizing olefins obtained by:(a) copulverizing a magnesium compoundcontaining halogen or a manganese compound containing halogen with atleast one electron-donor compound to produce a copulverized product, (b)treating the copulverized product with an ether to produce a treatedproduct, and (c) reacting the treated product with a titanium halidecompound.
 17. The component of claim 16 wherein the copulverizing step(a) is carried out in the presence of an effective amount of apulverization aid.
 18. The component of claim 17 wherein thepulverization aid is selected from the group consisting of hexane,heptane, kerosene, polystyrene, polypropylene, boron oxide, siliconoxide, and organopolysiloxanes.
 19. The component of claim 17 whereinthe effective amount is from about 0.001 to about 1 times the weight ofthe magnesium compound containing halogen or manganese compoundcontaining halogen.
 20. The component of claim 16 wherein the magnesiumcompound containing halogen is magnesium dichloride.
 21. The componentof claim 16 wherein at least one electron-donor compound is an aromaticcarboxylic acid employed in an amount of about 0.01 to about 1 mole ofacid per mole of magnesium compound containing halogen or manganesecompound containing halogen.
 22. The component of claim 16 wherein atleast one electron-donor compound is an acid selected from the groupconsisting of aliphatic carboxylic acids containing up to 18 carbonatoms, halogenated aliphatic carboxylic acids containing up to 18 carbonatoms, alicyclic carboxylic acids containing up to 12 carbon atoms, andaromatic carboxylic acids containing up to 24 carbon atoms.
 23. Thecomponent of claim 22 wherein at least one electron-donor compound is atoluic acid.
 24. The component of claim 16 wherein at least oneelectron-donor compound is ethyl benzoate.
 25. The component of claim 16wherein the ether is selected from the group consisting of aliphaticethers containing up to 12 carbon atoms, halogenated aliphatic etherscontaining up to 12 carbon atoms, aliphatic glycol ethers or half-etherscontaining up to 12 carbon atoms, alicyclic ethers containing up to 10carbon atoms, halogenated alicyclic ethers containing up to 10 carbonatoms, aromatic ethers containing up to 18 carbon atoms, and halogenatedaromatic ethers containing up to 18 carbon atoms.
 26. The component ofclaim 16 wherein the ether is a symmetrical aliphatic ether.
 27. Thecomponent of claim 26 wherein the symmetrical aliphatic ether isdi-n-butyl ether.
 28. The component of claim 16 wherein the titaniumhalide compound is titanium tetrachloride.
 29. The component of claim 16wherein the titanium halide compound is titanium trichloride material.30. The component of claim 16 wherein the quantity of titanium presentin the titanium halide is from about 0.1 percent to about 10 percent byweight expressed as elemental titanium.
 31. A process for producing acomponent containing titanium halide of a catalytic system forpolymerizing olefins comprising:(a) copulverizing a magnesium compoundcontaining halogen or a manganese compound containing halogen with atleast one electron-donor compound to produce a copulverized product, (b)treating the copulverized product with an ether to produce a treatedproduct, and (c) reacting the treated product with a titanium halidecompound.
 32. The process of claim 31 wherein the copulverizing step (a)is carried out in the presence of an effective amount of a pulverizationaid.
 33. The process of claim 31 wherein the pulverizing aid is selectedfrom the group consisting of hexane, heptane, kerosene, polystyrene,polypropylene, boron oxide, silicon oxide, and organopolysiloxanes. 34.The process of claim 31 wherein the effective amount is from about 0.001to about 1 times the weight of the magnesium compound containing halogenor manganese compound containing halogen.
 35. The process of claim 31wherein the magnesium compound containing halogen is magnesiumdichloride.
 36. The process of claim 31 wherein at least oneelectron-donor compound is an aromatic carboxylic acid employed in anamount of about 0.01 to about 1 mole of acid per mole of magnesiumcompound containing halogen or manganese compound containing halogen.37. The process of claim 31 wherein at least one electron-donor compoundis a toluic acid.
 38. The process of claim 31 wherein at least oneelectron-donor compound is ethyl benzoate.
 39. The process of claim 31wherein the ether is selected from the group consisting of aliphaticethers containing up to 12 carbon atoms, halogenated aliphatic etherscontaining up to 12 carbon atoms, aliphatic glycol ethers or half-etherscontaining up to 12 carbon atoms, alicyclic ethers containing up to 10carbon atoms, halogenated alicyclic ethers containing up to 10 carbonatoms, aromatic ethers containing up to 18 carbon atoms, and halogenatedaromatic ethers containing up to 18 carbon atoms.
 40. The process ofclaim 39 wherein the ether is a symmetrical aliphatic ether.
 41. Theprocess of claim 40 wherein the symmetrical aliphatic ether isdi-n-butyl ether.
 42. The process of claim 31 wherein the titaniumhalide compound is titanium tetrachloride.
 43. The process of claim 31wherein the titanium halide compound is titanium trichloride material.44. The process of claim 31 wherein the quantity of titanium present inthe titanium halide is from about 0.1 percent to about 10 percent byweight expressed as elemental titanium.